EP1905848B1 - Hot-rolled steel sheet excellent in painting bake hardenability and anti aging property at room temperature, and method of producing the same - Google Patents
Hot-rolled steel sheet excellent in painting bake hardenability and anti aging property at room temperature, and method of producing the same Download PDFInfo
- Publication number
- EP1905848B1 EP1905848B1 EP07118305A EP07118305A EP1905848B1 EP 1905848 B1 EP1905848 B1 EP 1905848B1 EP 07118305 A EP07118305 A EP 07118305A EP 07118305 A EP07118305 A EP 07118305A EP 1905848 B1 EP1905848 B1 EP 1905848B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hot
- steel sheet
- less
- room temperature
- rolled steel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910000831 Steel Inorganic materials 0.000 title claims description 69
- 239000010959 steel Substances 0.000 title claims description 69
- 230000003712 anti-aging effect Effects 0.000 title claims description 31
- 238000010422 painting Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 title claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000005098 hot rolling Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005246 galvanizing Methods 0.000 claims description 7
- 238000009864 tensile test Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 230000009466 transformation Effects 0.000 claims description 6
- 238000005275 alloying Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910000859 α-Fe Inorganic materials 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 17
- 229910052804 chromium Inorganic materials 0.000 description 10
- 229910052750 molybdenum Inorganic materials 0.000 description 10
- 229910052720 vanadium Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 229910001563 bainite Inorganic materials 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 229910000734 martensite Inorganic materials 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 229910001566 austenite Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910001567 cementite Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002171 field ion microscopy Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0224—Two or more thermal pretreatments
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0273—Final recrystallisation annealing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/939—Molten or fused coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
Definitions
- This invention relates to a steel sheet having painting bake hardenability (BH), anti-aging property at room temperature and formability at the same time, and a method of producing the steel sheet.
- BH painting bake hardenability
- the letters BH are an abbreviation of bake hardenability or bake hardening and it means a simplified evaluation, by means of a tensile test, of the increase in the mechanical strength of a steel sheet resulting from the baking of a painting after press forming in car manufacturing.
- BH is measured as follows: first, the flow stress of a steel sheet is measured under a 2% tensile deformation imposed at a tensile test; then, after a prescribed heat treatment (usually, at 170°C for 20 min., but heat treatments at 150°C and 160°C are also included in the present invention), the upper yield stress of the steel sheet is measured in another tensile test; suppose the flow stress at the first tensile test under the 2% tensile deformation-is ⁇ 1 and the upper yield stress at the second tensile test is ⁇ 2, the amount of BH is given as ⁇ 2 - ⁇ 1. Note that, when there is no upper yield point, the 0.2% proof stress of the steel sheet is used.
- a steel sheet according to the present invention is used for cars, home electric appliances, buildings, etc. and it includes hot-rolled steel sheet in the narrow sense of the word without surface treatment and a hot-rolled steel sheet in the broad sense of the word with surface treatment such as alloying hot dip galvanizing, electrolytic plating, etc. as an anti-corrosion measure.
- ultra low carbon steels The production of ultra low carbon steels has been made easier thanks to the latest technical advancement of the vacuum degassing treatment of molten steel, and the demands for ultra low carbon steels having excellent workability has been increasing.
- the ultra low carbon steel sheets containing Ti and Nb added in combination disclosed in Japanese Unexamined Patent Publication No. S59-31827 and the like, for example, have painting bake hardenability (BH) as well as extremely good workability, and are excellent also in hot dip galvanizing property. For this reason, these steel sheets have come to claim a significant position in the market.
- BH painting bake hardenability
- the amount of BH of the steel sheets is not beyond the level of those of conventional BH steel sheets, and they have a shortcoming that, when it is attempted to increase the amount of BH of the steel sheets, it becomes impossible to maintain their anti-aging property at room temperature.
- a steel sheet having an enhanced BH is excellent in workability thanks to its low strength at the stage of press forming, and is also excellent especially in dent resistance owing to the fact that it becomes hard after it is finally formed into the shape of a product component.
- the amount of solute C or solute N in steel is increased, the amount of BH is increased but, on the other hand, anti-aging property at room temperature poses a problem.
- Japanese Examined Patent Publication No. H3-2224 proposes a technology to obtain a cold-rolled steel sheet having a high r-value, high bake hardenability, good ductility and anti-aging property at room temperature at the same time, by adding a large amount of Nb, B and Ti, together, to an ultra low carbon steel so as to make the annealed structure of the steel a composite structure consisting of a ferrite phase and a phase formed through low temperature transformation.
- Japanese Unexamined Patent Publication No. H7-300623 teaches that it is possible to obtain both a high BH value and anti-aging property at room temperature, by increasing the carbon concentration at crystal grain boundaries of an ultra low carbon cold-rolled steel sheet containing Nb through controlling the cooling rate after annealing.
- the technology disclosed therein does not realize a high BH value and anti-aging property at room temperature in a sufficiently well-balanced manner.
- conventional BH steel sheets have shortcomings that stable production is difficult and that anti-aging property at room temperature is lost when the amount of BH is increased. Further, they have another problem in that a sufficient amount of BH is not obtained when the temperature at the baking of a painting is lowered from currently adopted 170°C to 160 or 150°C.
- EP-A-1 191 114 which is a prior art according to Art.54(3) EPC discloses a high tensile hot-rolled steel sheet having excellent strain aging hardening properties and method for producing the same in which Ti, Cr, Mo and V are not essential elements
- EP-A-1 028 167 which a prior art document according to Art.54(3) EPC discloses a high tensile strength hot-rolled steel sheet and method of producing the same in which Ti, Cr, Mo and V are not essential elements.
- EP-A-0 943 696 discloses steel plates for drum cans and method of manufacturing the same in which none of Cr, Mo and V is added to the steels.
- JP-A-07-316649 discloses a method for producing a hot-rolled steel plate excellent in workability and corrosion resistance in which no Ti is contained.
- JP-A-2000-54071 discloses a hot rolled thin steel sheet and its production in which an amount of solute N must be "0.0030% or more" and Cr, M, V and Ti are optional elements.
- the object of the present invention is to provide a steel sheet having both high bake hardenability and anti-aging property at room temperature and capable of maintaining a sufficient amount of BH even under a low BH temperature, and a method of producing the steel sheet.
- the present inventors discovered that it was possible, by adding Cr, Mo, V and so forth to a steel retaining solute N, to obtain both a high BH value and anti-aging property at room temperature and maintain high bake hardenability even when the baking of a painting was conducted at a lower temperature for a shorter period of time.
- the present invention is a totally new steel sheet which was hitherto unknown to the market, worked out on the basis of the philosophy and findings described above, and a method of producing the steel sheet.
- C is an element to increase steel strength economically, and its addition amount varies depending on the level of envisaged strength.
- decreasing the content of C to below 0.0001% is difficult for the reasons of steelmaking technology, and it not only incurs a cost increase but also deteriorates the fatigue property of welded portions.
- the lower limit of the addition amount of C is set at 0.0001%.
- the upper limit of the addition amount of C is, therefore, set at 0.20%.
- the amount of solute C is 0.0020% or less. Since high bake hardenability and anti-aging property at room temperature are secured according to the present invention mainly by means of the addition of N, when the amount of solute C is too large, it becomes difficult to maintain good anti-aging property at room temperature. It is more preferable to control the amount of solute C to below 0.0010%.
- the amount of solute C may be controlled by restricting the amount of total C to the upper limit specified above or less, otherwise by lowering it to the prescribed level through controlling the coiling temperature or the condition of the overaging treatment.
- Si is a solid solution hardening element and increases strength. It is also effective for forming a structure containing martensite, bainite and, in addition, a retained ⁇ phase and the like. While the addition amount of Si varies depending on the level of envisaged strength, when it exceeds 2.0%, press formability and a chemical treatment property are deteriorated. For this reason, the upper limit of the addition amount of Si is set at 2.0%. When an alloying hot dip galvanizing is applied, an addition of Si in a great amount results in problems such as low productivity caused by poorer plating adhesion and slower alloying reactions and, therefore, the upper limit of the Si content is set at 0.8%.
- No lower limit of Si is set specifically but, since lowering the Si content to 0.001% or less causes production cost increase, 0.001% is the lower limit in practical sense. If it is difficult to deoxidize steel with Al because of a requirement to control the amount of Al, Si may be used for deoxidation. In this case, 0.04% or more of Si is to be included in steel.
- Mn is useful as a solid solution hardening element. It is also effective for forming MnS to suppress the occurrence of edge cracks caused by S during hot rolling, fining the structure of hot-rolled sheets and forming the structure containing martensite, bainite and, in addition, a retained ⁇ phase and the like. Moreover, Mn has the effect to inhibit aging at room temperature caused by solute N. For these reasons, it is desirable to add 0.3% or more of Mn. When deep drawability is required, however, it is desirable to limit the content of Mn to 0.15% or less, preferably, to below 0.10%. When the addition amount of Mn exceeds 3.0%, on the other hand, the strength becomes so high that ductility is decreased and the plating adhesion of galvanizing is adversely affected. The upper limit of the addition amount of Mn is, therefore, set at 3.0%.
- P is known as an element to raise strength economically, like Si, thus, when it is necessary to increase strength, P is added intentionally. P also has the effects to make fine a hot-rolled structure and enhance workability. When it is added in excess of 0.15%, however, it deteriorates the fatigue strength after spot welding, and also increases yield strength too much causing poor planar shape at press forming. The excessive addition of P also lowers productivity since it drastically slows down the alloying reactions during continuous hot dip galvanizing, and the workability in secondary working is deteriorated, too. The upper limit of the addition of P is, therefore, set at 0.15%.
- the upper limit of the addition of S is set at 0.015%, since the addition of S in excess of 0.015% causes hot cracking and the deterioration of workability.
- Al may be added for oxidizing.
- Al combines with N to form AlN and, thus, lowers bake hardenability, it is desirable to limit its addition to the least necessary amount within the range not to make production technically difficult.
- an upper limit of the Al content may be 0.20%. Production is made easier still when the Al content is 0.05% or less or, more preferably, 0.02% or less.
- N is an important element in the present invention: good bake hardenability in the present invention is achieved mainly by using N. It is therefore essential to add 0.001% or more of N. When the content of N is too high, on the other hand, it becomes difficult to secure anti-aging property at room temperature, or workability is deteriorated. For this reason, the upper limit of the N content is set at 0.10%. A preferable range of the N content is from 0.002 to 0.020% or, more preferably, from 0.002 to 0.008%. Besides the above, because N easily combines with Al to form AlN, it is necessary to maintain the value of 0.52Al/N equal to or smaller than a prescribed value in order to secure a sufficient amount of N which contributes to the improvement of bake hardenability.
- the value of 0.52Al/N is defined as follows.
- the value of 0.52Al/N is 10 or more, AlN easily precipitates during the cooling and coiling after hot rolling and, for this reason, the upper limit of the value of 0.52Al/N has to be below 10.
- the value of 0.52Al/N is kept below 10, an excessive precipitation of AlN can be avoided by properly controlling the cooling rate and coiling temperature after hot rolling, and good bake hardenability can be realized.
- a more preferable upper limit of the value of 0.52Al/N is 5.
- Cr, Mo and V are important elements in the present invention; it is indispensable to add one or more of these elements to the steel. Good bake hardenability and anti-aging property at room temperature are obtained at the same time only when one or more of them are added.
- the present inventors noted as a new discovery that it was possible to obtain anti-aging property at room temperature without deteriorating bake hardenability, by adding Cr, Mo and/or V intentionally.
- N leaves of the pairs and clusters to fix dislocations, and this causes high bake hardenability to show.
- the upper limits of the addition amounts of Cr, Mo and V, which are determined in consideration of workability and production costs, are 2.5, 1.0 and 0.1%, respectively. When added too much, V forms nitrides and it becomes difficult to secure a sufficient amount of solute N. Therefore, it is desirable to limit the addition of V to 0.04% or less.
- the amount of solute N has to be 0.0005 to 0.004% in total.
- the solute N includes not only the N existing in Fe independently but also the N forming pairs or clusters with substitutional solute elements such as Cr, Mo, V, Mn, Si and P.
- the amount of solute N can be appropriately determined by the heating extraction method in a hydrogen gas flow. In the method, the amount of solute N is obtained by heating a sample to a temperature range from 200 to 500°C or so, forming ammonia through a reaction of the solute N with the hydrogen, analyzing the ammonia thus formed by mass spectrometry, and converting the amount of ammonia thus obtained.
- the amount of solute N can be calculated also by subtracting the amount of N existing as compounds such as AlN, NbN, VN, TiN, BN, etc. (determined through chemical analysis of the residue of the extraction) from the amount of total N. It may be obtained by the internal friction method or the field ion microscopy (FIM), too.
- Ca is effective for deoxidizing and also for controlling the shape of sulfides and, therefore, 0.0005 to 0.01% of Ca may be added. With an addition below 0.0005%, a sufficient effect is not obtained but, when added in excess of 0.01%, workability is deteriorated. For this reason, the range of the Ca addition has to be from 0.0005 to 0.01%.
- B is added, as required, by 0.0001 to 0.001% because it is effective for preventing the embrittlement of steel during secondary working. With an addition below 0.0001%, a tangible effect is not obtained and, when added in excess of 0.001%, however, the effect is saturated and, besides, BN is likely to form and it becomes difficult to secure a sufficient amount of solute N.
- a more preferable range of the B addition is from 0.0001 to 0.0004%.
- Nb is added, as required, within a range from 0.001 to 0.03%, as it is effective for enhancing workability and strength and also for forming a fine and homogeneous structure.
- the amount of its addition is below 0.001%, however, the effects of its addition do not show and, when added in excess of 0.03%, in contrast, NbN is likely to form and it becomes difficult to secure a sufficient amount of solute N.
- a more preferable range of the Nb addition is from 0.001 to 0.012%.
- Ti has the same effects as Nb and, for this reason, it is added within a range from 0.0001 to 0.10%.
- the amount of its addition is below 0.0001%, however, the effects do not show and, when added in excess of 0.10%, on the other hand, a large amount of N precipitates or crystallizes in the form of TiN and, thus, it becomes difficult to secure a sufficient amount of solute N.
- a preferable range of the Ti addition is from 0.001 to 0.020% or, more preferably, from 0.001 to 0.012%.
- Ti in order to secure a sufficient amount of solute N, Ti must be added within the range to satisfy the expression (N - 0.29Ti) > 0.0005 or, more preferably, (N - 0.29Ti) > 0.0010.
- a total of 0.001 to 1.0% of one or more of Sn, Cu, Ni, Co, Zn, W, Zr and Mg may be added to a steel containing the above elements as main components.
- Zr forms ZrN its addition is limited, desirably, to 0.01% or less.
- the slab to be hot-rolled is not restricted specifically in terms of its production conditions: it may be a continuously cast slab or a slab produced using a thin slab caster or the like.
- a slab produced by a process such as the continuous casting-direct rolling (CC-DR) process in which the slab is hot-rolled immediately after it is cast is also suitable for the present invention.
- the finishing temperature of the hot rolling must not be below the Ar 3 transformation temperature by 100°C or more. If the finishing temperature is below the Ar 3 transformation temperature by more than 100°C, it becomes difficult to obtain good workability or thickness accuracy.
- a more preferable finishing temperature range is the Ar 3 transformation temperature or higher. No upper limit is set specifically as to the finishing temperature of the hot rolling, but it is desirable that the temperature is 1,100°C or lower in order to prevent coarse crystal grains from forming and to protect the hot rolling rolls.
- the heating temperature of the hot rolling is not specifically restricted. But, when it is necessary to melt AlN in order to obtain a sufficient amount of solute N, it is desirable to heat a slab to 1,200°C or higher.
- the present inventors also discovered that, even when an excessive amount of N was added in proportion to Al, that is, even when the expression 0.52Al/N ⁇ 1 was true, it was essential, for securing high bake hardenability and anti-aging property at room temperature, to keep the cooling rate at 10°C/sec. or higher. It is more desirable for bake hardenability and anti-aging property at room temperature if the cooling rate is 30°C/sec. or higher. No upper limit of the cooling rate is set specifically, but it is desirable from the productivity viewpoint to cool the steel sheet at a cooling rate of 200°C/sec, or lower.
- the coiling temperature has to be 550°C or lower or, more desirably, 450°C or lower.
- the structure of the hot-rolled steel sheet obtained according to the present invention contains ferrite or bainite as the main phase, but it is acceptable if both of them exist as a mixture. It is also acceptable if martensite, austenite, carbides and/or nitrides exist in the mixture. This means that different structures may be formed in accordance with required characteristics.
- the value of BH170 of the steel sheet produced according to the present invention is 45 MPa or higher, and any of its BH160 and BH150 values is 35 MPa or higher. More preferable ranges are 60 MPa or higher for BH170 and 50 MPa or higher for both BH160 and BH150. No upper limits are set specifically for these values but, when the value of BH170 exceeds 140 MPa and those of BH160 and BH150 exceed 130 MPa, it becomes difficult to secure anti-aging property at room temperature.
- BH170 means the value of bake hardenability evaluated after applying a 2% tensile deformation and then a heat treatment at 170°C for 20 min.
- BH160 the value of bake hardenability evaluated after applying a 2% tensile deformation and then a heat treatment at 160°C for 10 min.
- BH150 the value of bake hardenability evaluated after applying a 2% tensile deformation and then a heat treatment at 150°C for 10 min.
- the anti-aging property at room temperature is evaluated in terms of the yield point elongation after an artificial aging treatment.
- the yield point elongation of the steel sheet produced according to the present invention at a tensile test after a heat treatment at 100°C for 1 h. is 0.6% or less.
- a preferable value is 0.4% or less or, more preferably, 0.3% or less.
- It is desirable that the yield point elongation after a heat treatment at 40°C for 70 days is 0.5% or less, preferably 0.3% or less or, more preferably, 0.2% or less.
- a hot-rolled steel sheet and a galvanized steel sheet having both good bake hardenability and anti-aging property at room temperature and capable of maintaining sufficient amount of bake hardenability even when the temperature of BH is low can be obtained by applying the present invention.
- the steel sheet according to the present invention is a steel sheet having painting bake hardenability, when it is used, its thickness can be made smaller than conventional steel sheets, which means that the weight of the products using the steel sheet can be reduced.
- the present invention is, therefore, considered to contribute to the conservation of the global environment.
- the steel sheet according to the present invention is excellent also in the collision energy absorption property and, consequently, contributes to enhancing the safety of a car.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Description
- This invention relates to a steel sheet having painting bake hardenability (BH), anti-aging property at room temperature and formability at the same time, and a method of producing the steel sheet..
- The letters BH are an abbreviation of bake hardenability or bake hardening and it means a simplified evaluation, by means of a tensile test, of the increase in the mechanical strength of a steel sheet resulting from the baking of a painting after press forming in car manufacturing. BH is measured as follows: first, the flow stress of a steel sheet is measured under a 2% tensile deformation imposed at a tensile test; then, after a prescribed heat treatment (usually, at 170°C for 20 min., but heat treatments at 150°C and 160°C are also included in the present invention), the upper yield stress of the steel sheet is measured in another tensile test; suppose the flow stress at the first tensile test under the 2% tensile deformation-is σ1 and the upper yield stress at the second tensile test is σ2, the amount of BH is given as σ2 - σ1. Note that, when there is no upper yield point, the 0.2% proof stress of the steel sheet is used.
- A steel sheet according to the present invention is used for cars, home electric appliances, buildings, etc. and it includes hot-rolled steel sheet in the narrow sense of the word without surface treatment and a hot-rolled steel sheet in the broad sense of the word with surface treatment such as alloying hot dip galvanizing, electrolytic plating, etc. as an anti-corrosion measure.
- The production of ultra low carbon steels has been made easier thanks to the latest technical advancement of the vacuum degassing treatment of molten steel, and the demands for ultra low carbon steels having excellent workability has been increasing. Among this kind of product, the ultra low carbon steel sheets containing Ti and Nb added in combination disclosed in Japanese Unexamined Patent Publication No.
S59-31827 - The amount of BH of the steel sheets, however, is not beyond the level of those of conventional BH steel sheets, and they have a shortcoming that, when it is attempted to increase the amount of BH of the steel sheets, it becomes impossible to maintain their anti-aging property at room temperature.
- A steel sheet having an enhanced BH is excellent in workability thanks to its low strength at the stage of press forming, and is also excellent especially in dent resistance owing to the fact that it becomes hard after it is finally formed into the shape of a product component. Generally speaking, when the amount of solute C or solute N in steel is increased, the amount of BH is increased but, on the other hand, anti-aging property at room temperature poses a problem.
- As an example of the technology related to a steel sheet having both high bake hardenability and anti-aging property at room temperature, Japanese Examined Patent Publication No.
H3-2224 - It has been made clear, however, that the proposed technology has problems related to actual production operation as described in 1) and 2) below.
- 1) In a steel having a composition comprising a large amount of Nb, B and Ti, the transformation point where the steel transforms from a phase to γ phase does not fall and thus annealing at a very high temperature is required for obtaining a composite structure, which in turn causes troubles such as strip breakage during continuous annealing.
- 2) Since the temperature range where the steel has an a+γ phase is very narrow, there arises the case that the structure varies along the width of the steel sheet resulting in the large dispersion of product quality or that the structure may or may not become a composite structure depending on the fluctuation of annealing temperature by several degrees Celsius. Therefore, the production tends to be very unstable.
- As another example, Japanese Unexamined Patent Publication No.
H7-300623 - There is another problem in conventional BH steel sheets that, whereas a prescribed amount of BH is obtained as far as the heat treatment of BH is conducted under a condition of 170°C for 20 min., the amount of BH is lowered under a heat treatment condition of 160°C for 10 min. or 150°C for 10 min.
- As described above, conventional BH steel sheets have shortcomings that stable production is difficult and that anti-aging property at room temperature is lost when the amount of BH is increased. Further, they have another problem in that a sufficient amount of BH is not obtained when the temperature at the baking of a painting is lowered from currently adopted 170°C to 160 or 150°C.
-
EP-A-1 191 114 which is a prior art according to Art.54(3) EPC discloses a high tensile hot-rolled steel sheet having excellent strain aging hardening properties and method for producing the same in which Ti, Cr, Mo and V are not essential elements -
EP-A-1 028 167 which a prior art document according to Art.54(3) EPC discloses a high tensile strength hot-rolled steel sheet and method of producing the same in which Ti, Cr, Mo and V are not essential elements. -
EP-A-0 943 696 discloses steel plates for drum cans and method of manufacturing the same in which none of Cr, Mo and V is added to the steels. -
JP-A-07-316649 -
JP-A-2000-54071 - The object of the present invention is to provide a steel sheet having both high bake hardenability and anti-aging property at room temperature and capable of maintaining a sufficient amount of BH even under a low BH temperature, and a method of producing the steel sheet.
- As a result of assiduous studies for achieving the above object, the present inventors obtained the following finding which was hitherto unknown.
- That is to say, the present inventors discovered that it was possible, by adding Cr, Mo, V and so forth to a steel retaining solute N, to obtain both a high BH value and anti-aging property at room temperature and maintain high bake hardenability even when the baking of a painting was conducted at a lower temperature for a shorter period of time.
- The present invention is a totally new steel sheet which was hitherto unknown to the market, worked out on the basis of the philosophy and findings described above, and a method of producing the steel sheet.
- The object above can be achieved by the features specified in the claims.
- The reasons why the chemical composition of steel and the production conditions are specified as above in the present invention will be explained in more detail hereafter.
- C is an element to increase steel strength economically, and its addition amount varies depending on the level of envisaged strength. However, decreasing the content of C to below 0.0001% is difficult for the reasons of steelmaking technology, and it not only incurs a cost increase but also deteriorates the fatigue property of welded portions. For this reason, the lower limit of the addition amount of C is set at 0.0001%. When the amount of C exceeds 0.20%, on the other hand, formability and weldability are adversely affected and, besides, it becomes difficult to obtain both good bake hardenability and anti-aging property at room temperature at the same time, which is a key issue in the present invention. The upper limit of the addition amount of C is, therefore, set at 0.20%. When the present invention is applied to the members to which deep drawing formability is required, it is preferable to control the content of C within a range from 0.0001 to 0.0020% or from 0.012 to 0.024%.
- It is desirable that the amount of solute C is 0.0020% or less. Since high bake hardenability and anti-aging property at room temperature are secured according to the present invention mainly by means of the addition of N, when the amount of solute C is too large, it becomes difficult to maintain good anti-aging property at room temperature. It is more preferable to control the amount of solute C to below 0.0010%. The amount of solute C may be controlled by restricting the amount of total C to the upper limit specified above or less, otherwise by lowering it to the prescribed level through controlling the coiling temperature or the condition of the overaging treatment.
- Si is a solid solution hardening element and increases strength. It is also effective for forming a structure containing martensite, bainite and, in addition, a retained γ phase and the like. While the addition amount of Si varies depending on the level of envisaged strength, when it exceeds 2.0%, press formability and a chemical treatment property are deteriorated. For this reason, the upper limit of the addition amount of Si is set at 2.0%. When an alloying hot dip galvanizing is applied, an addition of Si in a great amount results in problems such as low productivity caused by poorer plating adhesion and slower alloying reactions and, therefore, the upper limit of the Si content is set at 0.8%. No lower limit of Si is set specifically but, since lowering the Si content to 0.001% or less causes production cost increase, 0.001% is the lower limit in practical sense. If it is difficult to deoxidize steel with Al because of a requirement to control the amount of Al, Si may be used for deoxidation. In this case, 0.04% or more of Si is to be included in steel.
- Mn is useful as a solid solution hardening element. It is also effective for forming MnS to suppress the occurrence of edge cracks caused by S during hot rolling, fining the structure of hot-rolled sheets and forming the structure containing martensite, bainite and, in addition, a retained γ phase and the like. Moreover, Mn has the effect to inhibit aging at room temperature caused by solute N. For these reasons, it is desirable to add 0.3% or more of Mn. When deep drawability is required, however, it is desirable to limit the content of Mn to 0.15% or less, preferably, to below 0.10%. When the addition amount of Mn exceeds 3.0%, on the other hand, the strength becomes so high that ductility is decreased and the plating adhesion of galvanizing is adversely affected. The upper limit of the addition amount of Mn is, therefore, set at 3.0%.
- P is known as an element to raise strength economically, like Si, thus, when it is necessary to increase strength, P is added intentionally. P also has the effects to make fine a hot-rolled structure and enhance workability. When it is added in excess of 0.15%, however, it deteriorates the fatigue strength after spot welding, and also increases yield strength too much causing poor planar shape at press forming. The excessive addition of P also lowers productivity since it drastically slows down the alloying reactions during continuous hot dip galvanizing, and the workability in secondary working is deteriorated, too. The upper limit of the addition of P is, therefore, set at 0.15%.
- The upper limit of the addition of S is set at 0.015%, since the addition of S in excess of 0.015% causes hot cracking and the deterioration of workability.
- Al may be added for oxidizing. However, since Al combines with N to form AlN and, thus, lowers bake hardenability, it is desirable to limit its addition to the least necessary amount within the range not to make production technically difficult. In the case of a hot-rolled steel sheet, it is possible to secure a sufficient amount of solute N by rapid cooling after hot rolling, even when more Al than N is included in terms of the number of atoms. For this reason, an upper limit of the Al content may be 0.20%. Production is made easier still when the Al content is 0.05% or less or, more preferably, 0.02% or less.
- N is an important element in the present invention: good bake hardenability in the present invention is achieved mainly by using N. It is therefore essential to add 0.001% or more of N. When the content of N is too high, on the other hand, it becomes difficult to secure anti-aging property at room temperature, or workability is deteriorated. For this reason, the upper limit of the N content is set at 0.10%. A preferable range of the N content is from 0.002 to 0.020% or, more preferably, from 0.002 to 0.008%. Besides the above, because N easily combines with Al to form AlN, it is necessary to maintain the value of 0.52Al/N equal to or smaller than a prescribed value in order to secure a sufficient amount of N which contributes to the improvement of bake hardenability.
- In the case of a hot-rolled steel sheet, the value of 0.52Al/N is defined as follows. When the value of 0.52Al/N is 10 or more, AlN easily precipitates during the cooling and coiling after hot rolling and, for this reason, the upper limit of the value of 0.52Al/N has to be below 10. When the value of 0.52Al/N is kept below 10, an excessive precipitation of AlN can be avoided by properly controlling the cooling rate and coiling temperature after hot rolling, and good bake hardenability can be realized. A more preferable upper limit of the value of 0.52Al/N is 5.
- Cr, Mo and V are important elements in the present invention; it is indispensable to add one or more of these elements to the steel. Good bake hardenability and anti-aging property at room temperature are obtained at the same time only when one or more of them are added.
- It is known to be difficult to secure anti-aging property at room temperature when more than a prescribed amount of N is included in steel, because N diffuses more rapidly than C does. For this reason, BH steel sheets using N are not applied to the members for which appearance is important such as the outer panels of a car body.
- The present inventors, however, noted as a new discovery that it was possible to obtain anti-aging property at room temperature without deteriorating bake hardenability, by adding Cr, Mo and/or V intentionally.
- The mechanism through which the anti-aging property at room temperature is enhanced by one or more of these elements is not altogether clear, but it is speculated to be as follows.
- These elements form pairs and/or clusters together with N near room temperature, inhibiting the diffusion of N, and this secures anti-aging property at room temperature. During the baking treatment of painting at 150 to 170°C, in contrast, N leaves of the pairs and clusters to fix dislocations, and this causes high bake hardenability to show.
- The upper limits of the addition amounts of Cr, Mo and V, which are determined in consideration of workability and production costs, are 2.5, 1.0 and 0.1%, respectively. When added too much, V forms nitrides and it becomes difficult to secure a sufficient amount of solute N. Therefore, it is desirable to limit the addition of V to 0.04% or less.
- In order to secure anti-aging property at room temperature, Cr, Mo and/or V must be added so that the expression (Cr + 3.5Mo + 39V) ≧ 0.1 is satisfied. It is more desirable if the expression (Cr + 3.5Mo + 39v) ≧ 0.4 is satisfied. Further, for securing anti-aging property at room temperature, it is more effective to add two or more of Cr, Mo and V together than to add one of them individually.
- The amount of solute N has to be 0.0005 to 0.004% in total. Here, the solute N includes not only the N existing in Fe independently but also the N forming pairs or clusters with substitutional solute elements such as Cr, Mo, V, Mn, Si and P. The amount of solute N can be appropriately determined by the heating extraction method in a hydrogen gas flow. In the method, the amount of solute N is obtained by heating a sample to a temperature range from 200 to 500°C or so, forming ammonia through a reaction of the solute N with the hydrogen, analyzing the ammonia thus formed by mass spectrometry, and converting the amount of ammonia thus obtained.
- The amount of solute N can be calculated also by subtracting the amount of N existing as compounds such as AlN, NbN, VN, TiN, BN, etc. (determined through chemical analysis of the residue of the extraction) from the amount of total N. It may be obtained by the internal friction method or the field ion microscopy (FIM), too.
- When the amount of solute N is below 0.0012%, sufficient bake hardenability is not obtained. When the amount of solute N exceeds 0.003%, on the other hand, while bake hardenability is improved, it becomes difficult to obtain anti-aging property at room temperature.
- Ca is effective for deoxidizing and also for controlling the shape of sulfides and, therefore, 0.0005 to 0.01% of Ca may be added. With an addition below 0.0005%, a sufficient effect is not obtained but, when added in excess of 0.01%, workability is deteriorated. For this reason, the range of the Ca addition has to be from 0.0005 to 0.01%.
- B is added, as required, by 0.0001 to 0.001% because it is effective for preventing the embrittlement of steel during secondary working. With an addition below 0.0001%, a tangible effect is not obtained and, when added in excess of 0.001%, however, the effect is saturated and, besides, BN is likely to form and it becomes difficult to secure a sufficient amount of solute N. A more preferable range of the B addition is from 0.0001 to 0.0004%.
- Nb is added, as required, within a range from 0.001 to 0.03%, as it is effective for enhancing workability and strength and also for forming a fine and homogeneous structure. When the amount of its addition is below 0.001%, however, the effects of its addition do not show and, when added in excess of 0.03%, in contrast, NbN is likely to form and it becomes difficult to secure a sufficient amount of solute N. A more preferable range of the Nb addition is from 0.001 to 0.012%.
- Ti has the same effects as Nb and, for this reason, it is added within a range from 0.0001 to 0.10%. When the amount of its addition is below 0.0001%, however, the effects do not show and, when added in excess of 0.10%, on the other hand, a large amount of N precipitates or crystallizes in the form of TiN and, thus, it becomes difficult to secure a sufficient amount of solute N. A preferable range of the Ti addition is from 0.001 to 0.020% or, more preferably, from 0.001 to 0.012%. Besides the above, in order to secure a sufficient amount of solute N, Ti must be added within the range to satisfy the expression (N - 0.29Ti) > 0.0005 or, more preferably, (N - 0.29Ti) > 0.0010.
- A total of 0.001 to 1.0% of one or more of Sn, Cu, Ni, Co, Zn, W, Zr and Mg may be added to a steel containing the above elements as main components. However, since Zr forms ZrN, its addition is limited, desirably, to 0.01% or less.
- Next, the reasons why the production conditions are specified in the present invention will be explained.
- The slab to be hot-rolled is not restricted specifically in terms of its production conditions: it may be a continuously cast slab or a slab produced using a thin slab caster or the like. A slab produced by a process such as the continuous casting-direct rolling (CC-DR) process in which the slab is hot-rolled immediately after it is cast is also suitable for the present invention.
- In the case that a hot-rolled steel sheet is used as a final product, it is necessary to specify its production conditions as follows. The finishing temperature of the hot rolling must not be below the Ar3 transformation temperature by 100°C or more. If the finishing temperature is below the Ar3 transformation temperature by more than 100°C, it becomes difficult to obtain good workability or thickness accuracy. A more preferable finishing temperature range is the Ar3 transformation temperature or higher. No upper limit is set specifically as to the finishing temperature of the hot rolling, but it is desirable that the temperature is 1,100°C or lower in order to prevent coarse crystal grains from forming and to protect the hot rolling rolls.
- Note that the heating temperature of the hot rolling is not specifically restricted. But, when it is necessary to melt AlN in order to obtain a sufficient amount of solute N, it is desirable to heat a slab to 1,200°C or higher.
- After hot rolling, it is necessary to cool a hot rolled steel sheet so that an average cooling rate of 10°C/sec. or more is maintained from the finishing temperature of the hot rolling to at least 600°C, in order to suppress the precipitation of AlN.
- The present inventors also discovered that, even when an excessive amount of N was added in proportion to Al, that is, even when the expression 0.52Al/N < 1 was true, it was essential, for securing high bake hardenability and anti-aging property at room temperature, to keep the cooling rate at 10°C/sec. or higher. It is more desirable for bake hardenability and anti-aging property at room temperature if the cooling rate is 30°C/sec. or higher. No upper limit of the cooling rate is set specifically, but it is desirable from the productivity viewpoint to cool the steel sheet at a cooling rate of 200°C/sec, or lower.
- In order to suppress the precipitation of AlN, the coiling temperature has to be 550°C or lower or, more desirably, 450°C or lower.
- The structure of the hot-rolled steel sheet obtained according to the present invention contains ferrite or bainite as the main phase, but it is acceptable if both of them exist as a mixture. It is also acceptable if martensite, austenite, carbides and/or nitrides exist in the mixture. This means that different structures may be formed in accordance with required characteristics.
- It is acceptable to apply to the steel sheet after the hot rolling, as required, a pickling and then a skin-pass rolling, either in-line or off-line, at a reduction ratio of 10% or less or a cold rolling at a reduction ratio up to 40% or so.
- The value of BH170 of the steel sheet produced according to the present invention is 45 MPa or higher, and any of its BH160 and BH150 values is 35 MPa or higher. More preferable ranges are 60 MPa or higher for BH170 and 50 MPa or higher for both BH160 and BH150. No upper limits are set specifically for these values but, when the value of BH170 exceeds 140 MPa and those of BH160 and BH150 exceed 130 MPa, it becomes difficult to secure anti-aging property at room temperature.
- It has to be noted that; BH170 means the value of bake hardenability evaluated after applying a 2% tensile deformation and then a heat treatment at 170°C for 20 min.; BH160 the value of bake hardenability evaluated after applying a 2% tensile deformation and then a heat treatment at 160°C for 10 min.; and BH150 the value of bake hardenability evaluated after applying a 2% tensile deformation and then a heat treatment at 150°C for 10 min.
- The anti-aging property at room temperature is evaluated in terms of the yield point elongation after an artificial aging treatment. The yield point elongation of the steel sheet produced according to the present invention at a tensile test after a heat treatment at 100°C for 1 h. is 0.6% or less. A preferable value is 0.4% or less or, more preferably, 0.3% or less. It is desirable that the yield point elongation after a heat treatment at 40°C for 70 days is 0.5% or less, preferably 0.3% or less or, more preferably, 0.2% or less.
- Steels having the chemical compositions shown in Table 1 were produced and hot-rolled under the conditions shown in Table 2, wherein the slab heating temperature was 1,250°C for all the steels. After applying a skin-pass rolling at a reduction ratio of 1.0%, No. 5 test pieces specified in Japanese Industrial Standard (JIS No. 5 test pieces) were cut out, and the bake hardenability and the yield point elongation after an artificial aging treatment were measured. The structure of the steel sheets thus produced and their mechanical properties are shown in Table 2.
Table 2 steel Finishing Temperature Average cooling rate Coiling temperature Structure Solute N TS, YS, EI, BH170, BH160, BH150, *1 *2 °C °C/s °C % MPa MPa % MPa MPa MPa A 919 50 550 Single phase of Ferrite 0.0012 288 157 51 78 72 72 0.06 0.04 A 925 6 550 Single phase of Ferrite 0.0011 291 162 49 82 75 73 0.87 0.79 B 930 35 450 Single phase of Ferrite 0.0028 305 175 47 103 100 96 0.11 0.05 B 923 7 450 Single phase of Ferrite 0.0003 314 183 46 19 13 9 0 0 B 934 30 730 Single phase of Ferrite 0.0001 313 182 45 2 0 0 0 0 C 930 55 400 Ferrite + 95% bainitic ferrite 0.0068 376 238 42 119 112 110 0.39 0.28 D 902 35 500 Single phase of bainitic ferrite 0.0047 423 285 38 108 107 108 0.35 0.26 E 891 30 200 Ferrite + 82% bainitic ferrite 0.0014 466 301 35 86 84 84 0.11 0.04 E 888 7 450 Single phase of Ferrite 0.0012 449 280 37 92 85 81 1.86 1.83 F 932 40 500 Single phase of Ferrite 0.0000 295 154 53 5 2 1 0 0 G 922 40 730 Single phase of Ferrite 0.0000 292 160 52 58 42 29 0.65 0.65 H 930 20 500 Single phase of Ferrite 0.0011 286 149 54 65 57 55 0.88 0.81 I 936 50 400 Single phone of Ferrite 0.0018 357 196 44 90 80 78 2.14 2.04 J 931 30 500 Ferrite + cementite 0.0009 290 175 53 61 55 55 0 0 K 929 30 500 Ferrite + cementite 0.0011 298 180 52 64 53 49 0.77 0.78 L 906 40 550 Ferrite+ cementite 0.0034 341 209 44 107 103 105 0.37 0.32 M 914 21 Note 1) 150 Ferrite + 12% martensite + 1% bainite 0.0022 609 346 32 125 120 118 0.08 0.05 N 890 25 Note 2) 420 Ferrite + 7% austenite + 10% bainite 0.0017 614 7 413 37 90 90 87 0.19 0.14 O 860 22 3) Note 3) 430 Ferrite + 12% austenite + 11% bainite + 1% martensite 0.0010 835 502 32 94 89 87 0.11 0.07 P 860 Note 3) Note 3) 430 Ferrite + 10% austenite + 13% bainite 0.0007 840 520 31 76 71 72 0.94 0.92 *1: Yield point elongation (%) after heat treatment at 100°C for 1 hr.
*2: Yield point elongation (%) after heat treatment at 40°C for 70 days
Note 1) Cooled at 8°C/sec. down to 700°C after finish rolling, and at 60°C/sec. until coiling
Note 2) Cooled at 60°C/sec. down to 760°C after finish rolling, then at 6°C/sec. down to 700°C, and at 40°C/sec. until coiling
Note 3) Cooled at 60°C/sec. down to 710°C after finish rolling, then at 7°C/sec. down to 620°C, and at 50°C/sec. until coiling - A hot-rolled steel sheet and a galvanized steel sheet having both good bake hardenability and anti-aging property at room temperature and capable of maintaining sufficient amount of bake hardenability even when the temperature of BH is low can be obtained by applying the present invention.
- Since the steel sheet according to the present invention is a steel sheet having painting bake hardenability, when it is used, its thickness can be made smaller than conventional steel sheets, which means that the weight of the products using the steel sheet can be reduced. The present invention is, therefore, considered to contribute to the conservation of the global environment.
- Moreover, the steel sheet according to the present invention is excellent also in the collision energy absorption property and, consequently, contributes to enhancing the safety of a car.
Claims (3)
- A hot-rolled steel sheet excellent in painting bake hardenability and anti-aging property at room temperature characterized by: containing, in mass, 0.0001 to 0.20% of C, 2.0% or less of Si, 3.0% or less of Mn, 0.15% or less of P, 0.015% or less of S and, in addition, 0.20% or less of Al and 0.001 to 0.10% of N so as to satisfy the expression 0.52A1/N < 10 and, further, one or more of 2.5% or less of Cr, 1.0% or less of Mo and 0.1% or less of V so as to satisfy the expression (Cr + 3.5Mo + 39V) ≥0.4, 0.0001 to 0.10%, in mass, of Ti so as to satisfy the expression (N - 0.29Ti) > 0.0005, 0.0012 to 0.003%, in mass, of solute N, optionally one or more of 0.0005 to 0.01%, in mass, of Ca, 0.0001 to 0.001%, in mass, of B, and 0.001 to 0.03%, in mass, of Nb, further optionally one or more of Sn, Cu, Ni, Co, Zn, W, Zr and Mg to a total of 0.001 to 1.0% with the balance consisting of Fe and unavoidable impurities; having the value of BH170, which is evaluated after applying a 2% tensile deformation and then a heat treatment at 170°C for 20 min., equal to or more than 45 MPa, and any of the value of BH160, which is evaluated after applying a 2% tensile deformation and then a heat treatment at 160°C for 10 min., and the value of BH150, which is evaluated after applying a 2% tensile deformation and then a heat treatment at 150°C for 10 min., equal to or more than 35 MPa; and having the yield point elongation at a tensile test after applying a heat treatment at 100°C for 1 h. equal to or less than 0.6%.
- A galvanized hot-rolled steel sheet excellent in painting bake hardenability and anti-aging property at room temperature characterized by applying a hot dip galvanizing, an alloying hot dip galvanizing or an electrogalvanizing to a hot-rolled steel sheet according to claim 1.
- A method of producing a hot-rolled steel sheet excellent in painting bake hardenability and anti-aging property at room temperature characterized by: hot-rolling a slab having the chemical composition according to claim 1 at a temperature of 100°C below the Ar3 transformation temperature or higher; cooling the hot-rolled steel sheet thus produced from the hot rolling finishing temperature to a temperature of 600°C or below at an average cooling rate of 10°C/sec. or more; and then coiling it at a temperature of 550°C or below.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000237510A JP3958921B2 (en) | 2000-08-04 | 2000-08-04 | Cold-rolled steel sheet excellent in paint bake-hardening performance and room temperature aging resistance and method for producing the same |
EP01956779A EP1306456B1 (en) | 2000-08-04 | 2001-08-01 | Cold rolled steel sheet excellent in bake hardenability and resistance to ordinary temperature aging and method for their production |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01956779.1 Division | 2001-08-01 | ||
EP01956779A Division EP1306456B1 (en) | 2000-08-04 | 2001-08-01 | Cold rolled steel sheet excellent in bake hardenability and resistance to ordinary temperature aging and method for their production |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1905848A2 EP1905848A2 (en) | 2008-04-02 |
EP1905848A3 EP1905848A3 (en) | 2008-06-18 |
EP1905848B1 true EP1905848B1 (en) | 2012-01-25 |
Family
ID=18729356
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01956779A Expired - Lifetime EP1306456B1 (en) | 2000-08-04 | 2001-08-01 | Cold rolled steel sheet excellent in bake hardenability and resistance to ordinary temperature aging and method for their production |
EP07118305A Expired - Lifetime EP1905848B1 (en) | 2000-08-04 | 2001-08-01 | Hot-rolled steel sheet excellent in painting bake hardenability and anti aging property at room temperature, and method of producing the same |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01956779A Expired - Lifetime EP1306456B1 (en) | 2000-08-04 | 2001-08-01 | Cold rolled steel sheet excellent in bake hardenability and resistance to ordinary temperature aging and method for their production |
Country Status (7)
Country | Link |
---|---|
US (1) | US6706419B2 (en) |
EP (2) | EP1306456B1 (en) |
JP (1) | JP3958921B2 (en) |
KR (1) | KR100485659B1 (en) |
CN (1) | CN1147611C (en) |
DE (1) | DE60134025D1 (en) |
WO (1) | WO2002012580A1 (en) |
Families Citing this family (91)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002022893A1 (en) * | 2000-09-12 | 2002-03-21 | Kawasaki Steel Corporation | High tensile strength hot dip plated steel sheet and method for production thereof |
EP1637618B1 (en) * | 2003-05-27 | 2010-07-14 | Nippon Steel Corporation | Method for manufacturing high strength steel sheets with excellent resistance to delayed fracture after forming |
KR101125930B1 (en) * | 2003-12-04 | 2012-03-21 | 주식회사 포스코 | Non-aging cold rolled steel sheet having excellent resistance to second work embrittleness and high strength, process for producing the same |
KR101125974B1 (en) * | 2003-12-04 | 2012-03-19 | 주식회사 포스코 | Non-aging cold rolled steel sheet having excellent resistance to second work embrittleness and high strength, process for producing the same |
KR101125962B1 (en) * | 2003-12-05 | 2012-03-21 | 주식회사 포스코 | Non-aging cold rolled steel sheet having excellent recrstance to second work embrittlement and high strength, process for producing the same |
EP1689901B1 (en) | 2003-11-10 | 2018-03-21 | Posco | Cold rolled steel sheet having aging resistance and superior formability, and process for producing the same |
KR101126012B1 (en) * | 2003-12-04 | 2012-03-19 | 주식회사 포스코 | Non-aging cold rolled steel sheet having excellent recrstance to second work embrittlement and high strength, process for producing the same |
KR101143161B1 (en) * | 2003-11-19 | 2012-05-08 | 주식회사 포스코 | Cold rolled steel sheet having aging resistance and superior formability, and process for producing the same |
KR101143157B1 (en) * | 2003-12-08 | 2012-05-08 | 주식회사 포스코 | High strength cold rolled steel sheet having aging resistance and superior workability, and process for producing the same |
KR101143116B1 (en) * | 2003-12-22 | 2012-05-08 | 주식회사 포스코 | High strength cold rolled steel sheet having excellent resistance to second work embrittleness and aging resistance, and process for producing the same |
CN101372733B (en) * | 2003-12-23 | 2011-03-16 | Posco公司 | Bake-hardenable cold rolled steel sheet having excellent formability, and method of manufacturing the same |
US20070137739A1 (en) * | 2003-12-23 | 2007-06-21 | Jeong-Bong Yoon | Bake-hardenable cold rolled steel sheet having excellent formability, and method of manufacturing the same |
KR101115842B1 (en) * | 2004-10-21 | 2012-04-23 | 주식회사 포스코 | Bake hardening cold rolled steel sheet having superior workability and high strength, and process for producing the same |
KR101115763B1 (en) * | 2004-09-08 | 2012-03-06 | 주식회사 포스코 | Bake hardening cold rolled steel sheet having superior workability and high strength, and process for producing the same |
ES2389656T3 (en) * | 2003-12-23 | 2012-10-30 | Posco | Cold rolled and baked hardened steel sheet that has excellent formability, and method of manufacturing |
KR101105008B1 (en) * | 2003-12-29 | 2012-01-16 | 주식회사 포스코 | Bake-hardening cold rolled steel sheet having excellent formability and high strength, and method of manufacturing the same |
KR101143101B1 (en) * | 2003-12-29 | 2012-05-08 | 주식회사 포스코 | High strength cold rolled steel sheet having excellent resistance to second work embrittleness and aging resistance, and process for producing the same |
KR101105021B1 (en) * | 2003-12-29 | 2012-01-16 | 주식회사 포스코 | Bake-hardenable cold rolled having less anisotropy and high strength, and method of manufacturing the same |
KR101143032B1 (en) * | 2003-12-29 | 2012-05-08 | 주식회사 포스코 | Bake hardening cold rolled steel sheet having superior formability and high strength, and method of manufacturing the same |
KR101143083B1 (en) * | 2003-12-29 | 2012-05-08 | 주식회사 포스코 | Bake hardening cold rolled steel sheet having superior workability and high strength, and method of manufacturing the same |
KR101143039B1 (en) * | 2003-12-29 | 2012-05-08 | 주식회사 포스코 | High strength cold rolled steel sheet having aging resistance and superior workability, and process for producing the same |
KR101105055B1 (en) * | 2003-12-29 | 2012-01-16 | 주식회사 포스코 | Bake-hardenable cold rolled steel sheet having excellent resistance to second work embrittleness and high strength, and method of manufacturing the same |
KR101104976B1 (en) * | 2003-12-30 | 2012-01-16 | 주식회사 포스코 | Bake- hardening cold rolled steel sheet having high strength, method of manufacturing the same |
KR101105032B1 (en) * | 2003-12-30 | 2012-01-16 | 주식회사 포스코 | Bake hardenable cold rolled steel sheet having excellent formability and method of manufacturing the same |
KR101143061B1 (en) * | 2003-12-30 | 2012-05-08 | 주식회사 포스코 | Bake hardenable cold rolled steel sheet having superior fprmability and method of manufacturing the same |
JP4482360B2 (en) * | 2004-03-29 | 2010-06-16 | 新日本製鐵株式会社 | Cold-rolled steel sheet excellent in paint bake hardening performance and room temperature slow aging and method for producing the same |
KR101171113B1 (en) * | 2004-06-07 | 2012-08-03 | 주식회사 포스코 | High strength cold rolled steel sheet having excellent resistance to second work embrittleness and aging resistance, and process for producing the same |
KR101171114B1 (en) * | 2004-06-07 | 2012-08-03 | 주식회사 포스코 | High strength cold rolled steel sheet having excellent resistance to second work embrittleness and aging resistance, and process for producing the same |
KR101171112B1 (en) * | 2004-06-07 | 2012-08-03 | 주식회사 포스코 | Cold rolled steel sheet having excellent formability and aging resistance, and process for producing the same |
KR101143084B1 (en) * | 2004-11-23 | 2012-05-08 | 주식회사 포스코 | Cold rolled steel sheet having aging resistance superior workability and process for producing the same |
US7959747B2 (en) * | 2004-11-24 | 2011-06-14 | Nucor Corporation | Method of making cold rolled dual phase steel sheet |
US7442268B2 (en) * | 2004-11-24 | 2008-10-28 | Nucor Corporation | Method of manufacturing cold rolled dual-phase steel sheet |
US8337643B2 (en) | 2004-11-24 | 2012-12-25 | Nucor Corporation | Hot rolled dual phase steel sheet |
KR101143251B1 (en) * | 2004-11-25 | 2012-05-18 | 주식회사 포스코 | High strength cold rolled steel sheet having superior workability and process for producing the same |
KR101143240B1 (en) * | 2004-12-06 | 2012-05-18 | 주식회사 포스코 | Non aging cold rolled steel sheet having superior workability and process for producing the same |
KR101143098B1 (en) * | 2004-12-06 | 2012-05-08 | 주식회사 포스코 | High strength cold rolled steel sheet having aging resistance and superior workability, and process for producing the same |
KR101143107B1 (en) * | 2004-12-06 | 2012-05-08 | 주식회사 포스코 | Non aging cold rolled steel sheet having superior workability and high strength, and process for producing the same |
KR101143159B1 (en) * | 2004-12-06 | 2012-05-08 | 주식회사 포스코 | Non aging cold rolled steel sheet having superior workability and high strength, and process for producing the same |
WO2006118425A1 (en) * | 2005-05-03 | 2006-11-09 | Posco | Cold rolled steel sheet having superior formability and high yield ratio, process for producing the same |
EP1749895A1 (en) * | 2005-08-04 | 2007-02-07 | ARCELOR France | Manufacture of steel sheets having high resistance and excellent ductility, products thereof |
KR100711356B1 (en) * | 2005-08-25 | 2007-04-27 | 주식회사 포스코 | Steel Sheet for Galvanizing with Superior Formability and Method for Manufacturing the Steel Sheet |
JP5031751B2 (en) | 2005-09-23 | 2012-09-26 | ポスコ | Manufacturing method of high-strength cold-rolled steel sheet, hot-dipped steel sheet and cold-rolled steel sheet with excellent bake hardenability |
KR101099774B1 (en) | 2005-10-05 | 2011-12-28 | 신닛뽄세이테쯔 카부시키카이샤 | Cold-rolled steel sheet excellent in coating curability in baking and cold slow-aging property and process for producing the same |
SK288275B6 (en) * | 2005-12-01 | 2015-06-02 | Posco | Hot rolled steel sheet having excellent heat treatment and impact property, hot press parts made of it and the method for manufacturing thereof |
JP4804996B2 (en) * | 2006-04-07 | 2011-11-02 | 新日本製鐵株式会社 | Method for producing alloyed hot-dip galvanized steel sheet with good workability, powdering property and slidability |
CN100593709C (en) * | 2006-08-31 | 2010-03-10 | 宝山钢铁股份有限公司 | Stretching guide sample manufacturing method with top and bottom yield point |
US7608155B2 (en) * | 2006-09-27 | 2009-10-27 | Nucor Corporation | High strength, hot dip coated, dual phase, steel sheet and method of manufacturing same |
US11155902B2 (en) | 2006-09-27 | 2021-10-26 | Nucor Corporation | High strength, hot dip coated, dual phase, steel sheet and method of manufacturing same |
JP2007077510A (en) * | 2006-11-16 | 2007-03-29 | Jfe Steel Kk | High-strength high-ductility galvanized steel sheet excellent in aging resistance and its production method |
MX2019008366A (en) * | 2007-02-23 | 2019-09-16 | Tata Steel Ijmuiden Bv | Cold rolled and continuously annealed high strength steel strip and method for producing said steel. |
JP5135868B2 (en) * | 2007-04-26 | 2013-02-06 | Jfeスチール株式会社 | Steel plate for can and manufacturing method thereof |
EP1990431A1 (en) | 2007-05-11 | 2008-11-12 | ArcelorMittal France | Method of manufacturing annealed, very high-resistance, cold-laminated steel sheets, and sheets produced thereby |
JP4193998B1 (en) * | 2007-06-28 | 2008-12-10 | 株式会社神戸製鋼所 | Machine structural steel excellent in machinability and manufacturing method thereof |
AU2008311043B2 (en) * | 2007-10-10 | 2013-02-21 | Nucor Corporation | Complex metallographic structured steel and method of manufacturing same |
KR101042434B1 (en) * | 2007-10-29 | 2011-06-16 | 현대제철 주식회사 | A cold rolledsteel sheet and method for manufacturing the same |
KR100925639B1 (en) * | 2007-12-24 | 2009-11-06 | 주식회사 포스코 | High strength cold-rolled steel sheet having excellent weather resistance and method manufacturing the Same |
KR100957976B1 (en) * | 2007-12-26 | 2010-05-17 | 주식회사 포스코 | Cr-Nb Added Bake Hardenable Steel Sheet with Excellent Strain Aging Resistance and Manufacturing Method Thereof |
KR100957959B1 (en) * | 2007-12-26 | 2010-05-17 | 주식회사 포스코 | V-Zr Added Bake Hardenable Steel Sheet with Excellent Strain Aging Resistance and Manufacturing Method Thereof |
KR100978734B1 (en) * | 2008-03-07 | 2010-08-30 | 현대하이스코 주식회사 | Dual Phase Steel Sheet And Method For Manufacturing The Same |
CN102015155B (en) * | 2008-03-19 | 2013-11-27 | 纽科尔公司 | Strip casting apparatus with casting roll positioning |
US20090236068A1 (en) | 2008-03-19 | 2009-09-24 | Nucor Corporation | Strip casting apparatus for rapid set and change of casting rolls |
KR101130837B1 (en) | 2008-04-10 | 2012-03-28 | 신닛뽄세이테쯔 카부시키카이샤 | High-strength steel sheets which are extreamely excellent in the balance between burring workability and ductility and excellent in fatigue endurance, zinc-coated steel sheets, and processes for production of both |
US20090288798A1 (en) * | 2008-05-23 | 2009-11-26 | Nucor Corporation | Method and apparatus for controlling temperature of thin cast strip |
KR101228701B1 (en) * | 2009-03-24 | 2013-02-01 | 주식회사 포스코 | Bake Hardenable Steel Sheet with Excellent Strain Aging Resistance and Manufacturing Method Thereof |
KR101129757B1 (en) * | 2009-03-26 | 2012-03-23 | 현대제철 주식회사 | Method for preventing edge part saw type crack of thin slab |
EP2239351B1 (en) | 2009-04-09 | 2013-03-13 | Siemens Aktiengesellschaft | Introduction of at least one of the elements of hafnium, lanthanum and yttrium into a superalloy component |
EP2239346A1 (en) | 2009-04-09 | 2010-10-13 | Siemens Aktiengesellschaft | Slurry composition for aluminising a superalloy component |
JP5717631B2 (en) * | 2009-07-08 | 2015-05-13 | 東洋鋼鈑株式会社 | Cold-rolled steel sheet manufacturing method and cold-rolled steel sheet excellent in press formability |
KR100958019B1 (en) * | 2009-08-31 | 2010-05-17 | 현대하이스코 주식회사 | Dual phase steel sheet and method for manufacturing the same |
CN102791895B (en) * | 2009-12-04 | 2014-12-24 | Posco公司 | Cold rolled steel sheet for processing with excellent heat resistance, and preparation method thereof |
RU2463374C2 (en) * | 2010-08-09 | 2012-10-10 | Общество с ограниченной ответственностью "Северсталь-Проект" (ООО "Северсталь-Проект") | Steel and item made from it |
MX2013005311A (en) * | 2010-11-22 | 2013-06-13 | Nippon Steel & Sumitomo Metal Corp | Steel sheet of strain aging hardening type with excellent aging resistance after paint baking and process for producing same. |
CN102071357B (en) * | 2011-01-05 | 2013-07-31 | 武钢集团昆明钢铁股份有限公司 | Melting method of nitrogenous niobium vanadium microalloying 500MPa and 550MPa high-intensity aseismic reinforcing steel bar |
RU2478729C2 (en) * | 2011-05-20 | 2013-04-10 | Открытое акционерное общество "Северсталь" (ОАО "Северсталь") | Method of making steel strip (versions) |
JP2013064169A (en) * | 2011-09-15 | 2013-04-11 | Jfe Steel Corp | High-strength steel sheet and plated steel sheet excellent in bake-hardenability and formability, and method for production thereof |
JP2013072110A (en) * | 2011-09-27 | 2013-04-22 | Jfe Steel Corp | High-tensile, cold-rolled steel sheet excellent in surface quality after molding and method for manufacturing the same |
JP2013072107A (en) * | 2011-09-27 | 2013-04-22 | Jfe Steel Corp | Bake-hardenable, cold-rolled steel sheet excellent in surface quality after molding and method for manufacturing the same |
JP2013209725A (en) * | 2012-03-30 | 2013-10-10 | Jfe Steel Corp | Cold rolled steel sheet excellent in bendability and manufacturing method thereof |
PL2684975T3 (en) * | 2012-07-10 | 2017-08-31 | Thyssenkrupp Steel Europe Ag | Cold rolled steel flat product and method for its production |
WO2014069543A1 (en) * | 2012-10-30 | 2014-05-08 | 新日鐵住金ステンレス株式会社 | Ferritic stainless steel sheet having excellent heat resistance |
CN103849816B (en) * | 2012-12-04 | 2016-04-06 | 上海梅山钢铁股份有限公司 | Be applicable to gaily decorated basket bucket with having resisted stupefied soft tin-plate |
KR101505252B1 (en) * | 2012-12-26 | 2015-03-23 | 현대제철 주식회사 | Cold-rolled steel sheet for outcase of car having low yield ratio with excellent formability and method of manufacturing the same |
CN109023136A (en) * | 2013-09-19 | 2018-12-18 | 塔塔钢铁艾默伊登有限责任公司 | For hot formed steel |
CN104611632A (en) * | 2015-02-10 | 2015-05-13 | 苏州科胜仓储物流设备有限公司 | Wear-resistant and impact-resistant section bar for bracket beam and welding process thereof |
CN106498290B (en) * | 2016-10-13 | 2018-02-13 | 南京创贝高速传动机械有限公司 | A kind of corrosion resistant metal coating of gear case external surface |
CN106591699A (en) * | 2016-12-04 | 2017-04-26 | 丹阳市宸兴环保设备有限公司 | Rust-proof metal material for vehicle body |
CN106702266A (en) * | 2016-12-19 | 2017-05-24 | 本钢板材股份有限公司 | Ageing-resistant cold-rolled bake-hardening steel 220 BH and production method thereof |
CN106756554A (en) * | 2016-12-19 | 2017-05-31 | 本钢板材股份有限公司 | A kind of cold rolling baking hardened steel of resistance to timeliness 180BH and its production method |
US10633726B2 (en) * | 2017-08-16 | 2020-04-28 | The United States Of America As Represented By The Secretary Of The Army | Methods, compositions and structures for advanced design low alloy nitrogen steels |
CN108754328B (en) * | 2018-06-14 | 2020-01-07 | 鞍钢股份有限公司 | Normal-temperature aging resistant bake-hardened steel plate and manufacturing method thereof |
CN114411057B (en) * | 2021-12-30 | 2022-12-16 | 钢铁研究总院 | High-strength steel for core plate capable of sintering friction layer |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5544551A (en) * | 1978-09-25 | 1980-03-28 | Nippon Steel Corp | Production of low yield ratio high tension hot rolled steel plate of superior ductility |
JPS5931827A (en) | 1982-08-13 | 1984-02-21 | Nippon Steel Corp | Production of quench hardenable steel plate for ultra deep drawing |
JPS60145355A (en) * | 1984-01-06 | 1985-07-31 | Kawasaki Steel Corp | Low yield ratio high tension hot rolled steel sheet having good ductility without deterioration with age and its production |
JPS60174852A (en) | 1984-02-18 | 1985-09-09 | Kawasaki Steel Corp | Cold rolled steel sheet having composite structure and superior deep drawability |
JPH0238647B2 (en) * | 1985-05-10 | 1990-08-31 | Sumitomo Metal Ind | CHOKOCHORYOKUKOHANNOSEIZOHOHO |
JPH0730408B2 (en) * | 1987-04-02 | 1995-04-05 | 川崎製鉄株式会社 | Method for producing hot-rolled thin steel sheet having bake hardenability by normal temperature aging |
JPH0823048B2 (en) * | 1990-07-18 | 1996-03-06 | 住友金属工業株式会社 | Method for producing hot rolled steel sheet with excellent bake hardenability and workability |
CA2067043C (en) * | 1991-04-26 | 1998-04-28 | Susumu Okada | High strength cold rolled steel sheet having excellent non-aging property at room temperature and suitable for drawing and method of producing the same |
JP3294322B2 (en) * | 1992-06-05 | 2002-06-24 | 日新製鋼株式会社 | Method for producing hot-dip galvanized steel sheet for deep drawing with excellent paint bake hardenability and corrosion resistance |
JP3294321B2 (en) * | 1992-06-05 | 2002-06-24 | 日新製鋼株式会社 | Manufacturing method of cold-rolled steel sheet for deep drawing excellent in paint bake hardenability and corrosion resistance |
WO1994000615A1 (en) * | 1992-06-22 | 1994-01-06 | Nippon Steel Corporation | Cold-rolled steel plate having excellent baking hardenability, non-cold-ageing characteristics and moldability, and molten zinc-plated cold-rolled steel plate and method of manufacturing the same |
US5690755A (en) * | 1992-08-31 | 1997-11-25 | Nippon Steel Corporation | Cold-rolled steel sheet and hot-dip galvanized cold-rolled steel sheet having excellent bake hardenability, non-aging properties at room temperature and good formability and process for producing the same |
WO1994005823A1 (en) * | 1992-08-31 | 1994-03-17 | Nippon Steel Corporation | Cold-rolled sheet and hot-galvanized, cold-rolled sheet, both excellent in bake hardening, cold nonaging and forming properties, and process for producing the same |
JP2995526B2 (en) * | 1993-12-28 | 1999-12-27 | 新日本製鐵株式会社 | Manufacturing method of cold rolled steel sheet which has excellent formability, has paint bake hardenability, and has little fluctuation in paint bake hardenability in the width direction |
JP3002379B2 (en) | 1994-04-08 | 2000-01-24 | 新日本製鐵株式会社 | Manufacturing method of high-strength cold-rolled galvannealed steel sheets for automobiles with excellent formability, paint bake hardenability and little change in paint bake hardenability |
JP3140289B2 (en) * | 1994-04-08 | 2001-03-05 | 新日本製鐵株式会社 | Method for manufacturing high-strength cold-rolled steel sheet for automobiles that has excellent formability, has paint bake hardenability, and has little variation in paint bake hardenability in the width direction. |
JP3569949B2 (en) | 1994-05-02 | 2004-09-29 | Jfeスチール株式会社 | Method of manufacturing thin steel sheet for processing with excellent bake hardenability and aging resistance |
JP3550729B2 (en) * | 1994-05-20 | 2004-08-04 | 住友金属工業株式会社 | Manufacturing method of hot rolled steel sheet with excellent formability, corrosion resistance and bake hardening ability |
JPH08143953A (en) * | 1994-11-15 | 1996-06-04 | Nisshin Steel Co Ltd | Production of aging resisting hot rolled steel plate of baking hardening type |
CN1092714C (en) * | 1997-09-04 | 2002-10-16 | 川崎制铁株式会社 | Steel plates for drum cans, method of manufacturing same, and drum can |
JP2000054071A (en) * | 1998-07-30 | 2000-02-22 | Kawasaki Steel Corp | Hot rolled thin steel sheet and its production |
CA2297291C (en) * | 1999-02-09 | 2008-08-05 | Kawasaki Steel Corporation | High tensile strength hot-rolled steel sheet and method of producing the same |
WO2001062997A1 (en) * | 2000-02-23 | 2001-08-30 | Kawasaki Steel Corporation | High tensile hot-rolled steel sheet having excellent strain aging hardening properties and method for producing the same |
-
2000
- 2000-08-04 JP JP2000237510A patent/JP3958921B2/en not_active Expired - Fee Related
-
2001
- 2001-08-01 WO PCT/JP2001/006635 patent/WO2002012580A1/en active IP Right Grant
- 2001-08-01 DE DE60134025T patent/DE60134025D1/en not_active Expired - Lifetime
- 2001-08-01 EP EP01956779A patent/EP1306456B1/en not_active Expired - Lifetime
- 2001-08-01 US US10/110,163 patent/US6706419B2/en not_active Expired - Lifetime
- 2001-08-01 EP EP07118305A patent/EP1905848B1/en not_active Expired - Lifetime
- 2001-08-01 CN CNB01802288XA patent/CN1147611C/en not_active Expired - Fee Related
- 2001-08-01 KR KR10-2002-7004421A patent/KR100485659B1/en active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
DE60134025D1 (en) | 2008-06-26 |
JP2002053933A (en) | 2002-02-19 |
EP1905848A2 (en) | 2008-04-02 |
KR20020035653A (en) | 2002-05-13 |
CN1386142A (en) | 2002-12-18 |
US20020197508A1 (en) | 2002-12-26 |
EP1306456B1 (en) | 2008-05-14 |
CN1147611C (en) | 2004-04-28 |
EP1306456A4 (en) | 2005-02-16 |
WO2002012580A1 (en) | 2002-02-14 |
US6706419B2 (en) | 2004-03-16 |
EP1306456A1 (en) | 2003-05-02 |
EP1905848A3 (en) | 2008-06-18 |
JP3958921B2 (en) | 2007-08-15 |
KR100485659B1 (en) | 2005-04-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1905848B1 (en) | Hot-rolled steel sheet excellent in painting bake hardenability and anti aging property at room temperature, and method of producing the same | |
EP2415893B1 (en) | Steel sheet excellent in workability and method for producing the same | |
EP1979500B1 (en) | High manganese steel strips with excellent coatability and superior surface property, coated steel strips using steel strips and method for manufacturing the steel strips | |
EP3221476B1 (en) | Method for manufacturing a high strength steel product and steel product thereby obtained | |
EP1642990B1 (en) | High strength steel plate excellent in formability and method for production thereof | |
EP2762581B1 (en) | Hot-rolled steel sheet and method for producing same | |
EP3730636B1 (en) | High-strength steel sheet having excellent processability and method for manufacturing same | |
KR101607041B1 (en) | Method for producing high-strength cold-rolled steel sheet having excellent anti-aging property and bake hardening property | |
EP2290111A1 (en) | Dual phase steel sheet and method of manufacturing the same | |
EP3730635A1 (en) | High-strength steel sheet having excellent impact properties and formability and method for manufacturing same | |
EP2623622B1 (en) | High-strength hot-dip galvanized steel sheet with excellent deep drawability and stretch flangeability, and process for producing same | |
EP2604715A1 (en) | High-strength cold-rolled steel sheet having excellent workability and impact resistance, and method for manufacturing same | |
EP2309012A1 (en) | High yield ratio and high-strength cold rolled thin steel sheet superior in weldability and ductility, high-yield ratio high-strength hot-dip galvanized cold rolled thin steel sheet, high-yield ratio high-strength hot-dip galvannealed cold rolled thin steel sheet, and methods of production of same | |
US20240327961A1 (en) | High strength cold rolled steel strip sheet for automotive use having good withstandability to retained austentite decomposition | |
EP3561121A1 (en) | Cold-rolled steel sheet having excellent bendability and hole expandability and method for manufacturing same | |
EP3901313A1 (en) | High-strength cold-rolled steel sheet having excellent bending workability and manufacturing method therefor | |
JPH06145891A (en) | High strength cold rolled steel sheet excellent in ductility and delayed fracture resistance and its production | |
JP4436348B2 (en) | Hot-rolled steel sheet excellent in paint bake-hardening performance and room temperature aging resistance and method for producing the same | |
EP1932932A1 (en) | Cold-rolled steel sheet excellent in coating curability in baking and cold slow-aging property and process for producing the same | |
EP3889277B1 (en) | High-strength steel sheet and method for manufacturing the same | |
JPH06145893A (en) | High strength galvanized steel sheet excellent in ductility and delayed fracture resistance and its production | |
EP4194578A1 (en) | High-strength cold rolled steel sheet, high-strength plated steel sheet, method for manufacturing high-strength cold rolled steel sheet, and method for manufacturing high-strength plated steel sheet | |
EP2980227A1 (en) | Steel sheet and method for producing same | |
KR102379444B1 (en) | Steel sheet having excellent formability and strain hardening rate and method for manufacturing thereof | |
US20240229184A1 (en) | Coiling temperature influenced cold rolled strip or steel |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20071108 |
|
AC | Divisional application: reference to earlier application |
Ref document number: 1306456 Country of ref document: EP Kind code of ref document: P |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA HR MK YU |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA HR MK RS |
|
17Q | First examination report despatched |
Effective date: 20080905 |
|
AKX | Designation fees paid |
Designated state(s): DE FR GB NL |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RTI1 | Title (correction) |
Free format text: HOT-ROLLED STEEL SHEET EXCELLENT IN PAINTING BAKE HARDENABILITY AND ANTI AGING PROPERTY AT ROOM TEMPERATURE, AND METHOD OF PRODUCING THE SAME |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AC | Divisional application: reference to earlier application |
Ref document number: 1306456 Country of ref document: EP Kind code of ref document: P |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB NL |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: NIPPON STEEL CORPORATION |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: T3 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 60146046 Country of ref document: DE Effective date: 20120322 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20121026 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 60146046 Country of ref document: DE Effective date: 20121026 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 60146046 Country of ref document: DE Representative=s name: VOSSIUS & PARTNER, DE Effective date: 20130227 Ref country code: DE Ref legal event code: R081 Ref document number: 60146046 Country of ref document: DE Owner name: NIPPON STEEL & SUMITOMO METAL CORPORATION, JP Free format text: FORMER OWNER: NIPPON STEEL CORP., TOKIO/TOKYO, JP Effective date: 20130227 Ref country code: DE Ref legal event code: R082 Ref document number: 60146046 Country of ref document: DE Representative=s name: VOSSIUS & PARTNER PATENTANWAELTE RECHTSANWAELT, DE Effective date: 20130227 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: CD Owner name: NIPPON STEEL & SUMITOMO METAL CORPORATION, JP Effective date: 20130913 Ref country code: FR Ref legal event code: CA Effective date: 20130913 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 16 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 17 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 18 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 60146046 Country of ref document: DE Representative=s name: VOSSIUS & PARTNER PATENTANWAELTE RECHTSANWAELT, DE Ref country code: DE Ref legal event code: R081 Ref document number: 60146046 Country of ref document: DE Owner name: NIPPON STEEL CORPORATION, JP Free format text: FORMER OWNER: NIPPON STEEL & SUMITOMO METAL CORPORATION, TOKYO, JP |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20190712 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20190716 Year of fee payment: 19 Ref country code: FR Payment date: 20190711 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20190731 Year of fee payment: 19 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60146046 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20200901 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20200801 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210302 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200801 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200901 |